Mineral oil lubricant containing phosphorized and sulfurized glyceryl trioleate



Patented Feb. 20, 1951 MINERAL. OIL LUBRICANT CONTAINING PH OSRHORIZED AND SULFURIZED; GLYC-ERYL TRIOLEATE':

Jos'e' ih B. stuck'er, Oak Par-K111i,- assi'girdr to The;

Pure; Oil? Company, Chicago; Ill., a" corporation.

of Ohio NoDrawi'ng-g Applicationf'lfiafch ;1946; SerialNo. 653,438

8JC1aims". (01. 252-4) This; invention relates tolubri'cants and lubrican't additives andi more particularly to addi tives which have the'ability'to carry high loads; and which when blended: with mineral lubricating, oils give blends having: low pour,v characteris tics.

. In Patent No. 2,211,306: there is; disclosed and claimed alprocess for making an extreme" pressure lubricant additive by sulfurizing a fatty body or fatty oil,v and. then phosphorizingi the sulfurized product; Extreme pressure additivesmadein accordance with the aforesaid. patent havebeen in successful use for many yearsand have proved to be highly satisfactory. Such additives'when made fromordinar-y: fatty oil,- such as lard oil, have. one drawback,.- namely, that the: lubricant which. results from blending the add-i tive with the. mineral oil does not have a: sumciently low pounpoint.

I have discovered that sulfurized and phosphorized extreme pressure'additives'having high-load carrying characteristics and-lowpour point characteristics. can be prepared inaccordance. withthe method disclosed: and claimed. in Patent No: 2,211,306 ifi thefatty-body is an ester ofapolyhy droxyalcohol-and. a mono-ethenoidacidof the general ff1'111l13CnH2w-202 containing from 10- to' 24 carbon atoms in the molecule; As examples of esters-which are suitab.e in preparing additives. in accordance with my invention; may

be mentioned polyhydric alcohol esters of deceenoic, myristoleic, pal'mitoleic, oleic; erucic; and tetracosenoic acids c ombinedi-with-any one oftth'el: polyhydroxy alcohols, glycol} glyceryl" and:sorbitol." Although. I. prefer those; esters: which are completely esterified, esters in which ionly partial esterifi'cation has taken place are al so suitable z asin'gl'e double bo'nd'a are hydrogenated to" as'i'n-*' gle' doublei bo1id radical may be used. Olive oil is fairly satisfactory as a star-ting material In general; the: fatty acid content of compositions useful: as" starting materials in' accordanc with; my invention should not be less than8075 of mono ethenoid acids and: not more; than 10 of acids? of greater unsaturation;

order to demonstrate the' invention a com position was prep'aredby'mixingfi parts byweig'ht of Gulf Coastmineraloil (having a Sayboltvis cosity at IOO F. of 200 to=-210 seconds, and at 210 of: 43 tool-5 seconds) and 87i6parts' by weight" of glyce'ryloleates composed" ofapproximately" For example. the mono-, diand=tri-esters-of glycerol, or mixtures of the three may bezusedi Instead of using pure esters. of. polyhydroxy alcohols and mono-ethenoidl acids; compositions; maybe used? which aresubstantially free of or containvery small amounts'v'ofpolyethenoidtacids or? esters thereof and a small: amount. of ethenoid' radicals. For example, partially hydrogenated sunflower, corn and rape seed oil in which the hydrogenation is carrie'dT'to a point only where the acid radicalsihaving morelunsatura'tion than by weight of glyceryl triole'ate, 20% by weight of glyceryl diol'eate' and 10%: by weight ofi-glyc'eryl mono-ole'atei The mixture was slowly heated to a temperature of approximately 270" whereupon 71% parts by Weightof finely ground flowers of sulfur were: added over a" period of about-1 0 minutes. After'the addition of the:sul-" fur was completed the mixture was raised to a temperature" of-v approximately 330 to 340 F. and held at -this temperature with constant" agitation until' a, copper strip immersed therein for a'aperiod of Z minutesT showed no black coating. This? requiredapproximately 7 hours. The mix turewas: then" cooledrapidly to approximately" 150 Fnand' then allowed to-cool' slowly to room temperature: To'99z6 partsof thesulfurized base thus prepared was-added 0:4 p'artbv weight of; finely divided phosphorus sesqu-isufideandthe mixture heated with. constant agitation to a? temperature: of. approximately 220 to 230 F1 Theaheating was continued for a period of approximately5 hours and then allowed to cool.- The: resulting product was non-corrosiveto the copper strip test and" did not fume: when heated to: 300 to- 350-? F.: Theresulting product was blended in the amount of 18% by Weight-with mineral-oibinorder to obtain apblend correspondto an S; A}: gravity oil, and-another corresponding toa90 S. -A. E. g ravityoil. These blen'ds were: tested for viscosity, viscosity index}: pour point, and: Timken test and compared with similar blends of phosphorized-sulfurized lard" oil; made.iniaccordancewith thespecificexample fiet/ibrtln in: the =mannen just-described in wh h?" glyceryl oleates were used. The results of these tests are set forth in the following table:

4 approximately 0.5 to 20% or more by weight of the finished lubricant. The amount will depend Table Saybolt Saybolt Composition by Wt. Vis. at Vis. at V. 1. Pour Timkeu Test 187 3-? Lard Oil t 419?, 100 Gulf Coast Pale Ol]. 353 59. 8 116 +10 71 lbs., 39,500 p. s. 1. 56. 8 123 30 771135., 39,500 p. S. i.

- 91.1 79 681bs.,35,000 p. s. i. 41% E60 vi1s.'-'@ 21101G11i Coast bright stock 18] -P g ycery 0 ea c 63 7; 200 Gulf Coast Pale i 924 86.1 98 20 86 lbs., 38,000 p. s. i.

O l 19% 160 vis. 210 Gulf Coast bright stock From an inspection of the table it is apparent that the blends made by sulfurizing and phosphorizing the glyceryl oleate had higher viscosity general, were superior from a load carrying standpoint.

Blends prepared in accordance with: the sec-.1.

0nd and fourth samples in the table were subjected to actual service tests in the transmission and differential of a number'of different automobiles. After 4,000 to 5,000 miles running the gears showed no evidence of wear, and the lubricant exhibited'high stability. Low temperature characteristics of the lubricant were excellent as evidenced by the fact that after the automobile had been allowed to stand outdoors at tempera-' tures approaching F. the gears could'be shifted with ease.

'In preparing the additive in accordance with' my invention sulfurization may be effected by means of elemental sulfur in an amount of from 1 to 10% by weight, and preferably 5 to 8.5% by weight of sulfur ba ed on the sulfurized product, or by means of sulfur chloride in accordance with the method di clo ed in Patent No. 2,352,818 in the amount of approximately 5 to by weight of the sulfur chloride based on the e ter.

tures of about 220 to 230 F., but other phosphorus compounds, including halides such as phosphorus trichloride. oxyhalides such as phos-I phorus oxychloride, sulfides, such as phosphorus pentasulfide. oxides such as pho phorus pent oxide. as well as elemental phosphorus compounds The phosphorization step is preferably effected by r means of phosphorus se quisulfide at temperaupon the service for which the lubricant is intended. Although additives prepared in accordance with my invention may be blended with all types of mineral lubricating oil, prefer to keep the amount of Pennsylvania bright stock present in the blend to a minimum sincethese stocks tendto cause separation of the additive from the oil.

It is claimed:

1. A lubricant additive substantially consisting ofthe reaction product of phosphorus sesquisulfide and sulfurized glyceryl oleates, at least 70% of said glyceryl oleates being glyceryl trioleate, the

sulfur content of said additiveib'eing about 1 to 10 .iper cent, andthe phosphorusrontent thereof 5 being about 0.2 to 0.6 per cent by weight. 7

"21A lubricant additive in accordance with per cent by weight. Y

A lubricant additive in accordance with claim 1 in which the glyceryl oleates are composed of mono-, diand tri-glyceryl oleates.

4. A lubricant additive substantially consisting of the product resulting from the reaction of sul-' fur and glyceryl oleates containing at least 70% of glyceryl trioleate, followed' by reaction with phosphorus sesquisulfide, said product contain-- ing about 5 to 8.5 per cent by weight of sulfur and about 0.2 to 0.6 per cent by weight of phosphorus.

5. A lubricant additive substantially consisting of the product resulting from the reaction of about 5 parts by weight of mineral lubricating oil,

87.5 parts by weight of glyceryl oleates containing at least 70% of glyceryl trioleate, and 7.4

parts by Weight of sulfur, followed by reaction with about 0.4 part by weight of phosphorus sesq'uisulfide.

6. A mineral lubricating oil containing as the principal extreme pressure additive from 0.5 to

20 per cent by weight of th additive defined by claim 1', said oil having the ability to flow at temperatures approaching l0ff, F.

7. A'lubricating oil of SQQIA. E. 80 grade com- -posed of Gulf Coast lubricating oil to which has such as tin phosphide, may be used. The amount 1 of phos horus in the ba e should not exceed 2%,

and preferably should be only a fraction of 1%,

preferably 0.2 to 0.6% based on the wegiht of the sulfurized base.

It will be seen, therefore, that by sulfurizing and phosphorizing a fatty body composed chiefly. of esters of polyhydroxy alcohols and monoethenoid acids a lubricant additive having high load characteri tics and unexpected low temperature characteristics can be obtained. Additives made in accordance with my invention may be used in lubricating oils in amounts ranging from been added as the principal extreme pressure additive from 0.5 to 20 per cent of the additive:

defined by claim 1, said oil having a pour point of about 30 F.

e. A lubricating oil of s n- E. 90 grade com- 7 posed of Gulf Coast lubricating oil containing as the principal extreme pressure additive from 0.5

to 20 per cent by weight of the'additive defined by claim 1, said oil having a pour point of about JOSEPH B. STUCKER.

(References on following pagel claim 1 in which the sulfur content is 5 to 8.5

The following references are of record in the REFERENCES CITED file of this patent:

UNITED STATES PATENTS Number Number 6 Name Date Morway et a1. Nov. 18, 1941 Roehner et a1, Jan. 12, 1943 Prutton Aug. 8, 1944 Musselman May 18, 1948 Musselman Sept. 6, 1949 Brennan Oct. 4, 1949 

1. A LUBRICANT ADDITIVE SUBSTANTIALLY CONSISTING OF THE REACTION PRODUCT OF PHOSPHORUS SESQUISULFIDE AND SULFURIZED GLYCERYL OLEATES, AT LEAST 70% OF SAID GLYCERYL OLEATES BEING GLYCERYL TRIOLEATE, THE SULFUR CONTENT OF SAID ADDITIVE BEING ABOUT 1 TO 10 PER CENT, AND THE PHOSPHORUS CONTENT THEREOF BEING ABOUT 0.2 TO 0.6 PER CENT BY WEIGHT. 